A straightforward methodology for the assembly of polysubstituted naphthalenes from ortho -alkynyl benzyl alcohols, enabled by using catalytic amounts of Tf 2 O, has been developed. This transformation not only features transition-metal free and without using other bases and additives but also provides a new synthetic application for ortho -alkynyl benzyl alcohols, i.e., as C6 synthons for the construction of PAHs.